CN104513280A - Bridged dinuclear metallocene compound for sPP , and preparation method and application thereof - Google Patents
Bridged dinuclear metallocene compound for sPP , and preparation method and application thereof Download PDFInfo
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- CN104513280A CN104513280A CN201410820139.0A CN201410820139A CN104513280A CN 104513280 A CN104513280 A CN 104513280A CN 201410820139 A CN201410820139 A CN 201410820139A CN 104513280 A CN104513280 A CN 104513280A
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- China
- Prior art keywords
- fluorenes
- zrcl
- lithium
- spp
- metallocene compound
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Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 31
- 239000003446 ligand Substances 0.000 claims abstract description 27
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 20
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 20
- -1 methylene, ethyl Chemical group 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000460 chlorine Substances 0.000 claims abstract description 14
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 121
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 66
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 229910007926 ZrCl Inorganic materials 0.000 claims description 33
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 239000012074 organic phase Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 10
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 8
- 210000003097 mucus Anatomy 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 125000003250 fulvenyl group Chemical class C1(=CC=CC1=C)* 0.000 claims 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract 2
- XTCAGVVVEIJFON-UHFFFAOYSA-N 9h-fluorene;lithium Chemical compound [Li].C1=CC=C2CC3=CC=CC=C3C2=C1 XTCAGVVVEIJFON-UHFFFAOYSA-N 0.000 abstract 1
- MDQUTQCPJZOGGT-UHFFFAOYSA-N lithium;9h-fluoren-9-ide Chemical compound [Li+].C1=CC=C2C3=CC=CC=C3[CH-]C2=C1 MDQUTQCPJZOGGT-UHFFFAOYSA-N 0.000 abstract 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000126 substance Substances 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 21
- 229960004132 diethyl ether Drugs 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000006228 supernatant Substances 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- 150000002220 fluorenes Chemical group 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- JAZNSOPOXXXZQO-UHFFFAOYSA-N [N].CCO Chemical compound [N].CCO JAZNSOPOXXXZQO-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000007172 homogeneous catalysis Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 125000000950 dibromo group Chemical group Br* 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 5
- 150000002234 fulvenes Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- WTPWAEBALYUUPC-UHFFFAOYSA-N 2,7-ditert-butyl-9h-fluorene;lithium Chemical compound [Li].CC(C)(C)C1=CC=C2C3=CC=C(C(C)(C)C)C=C3CC2=C1 WTPWAEBALYUUPC-UHFFFAOYSA-N 0.000 description 2
- WXACXMWYHXOSIX-UHFFFAOYSA-N 5-propan-2-ylidenecyclopenta-1,3-diene Chemical compound CC(C)=C1C=CC=C1 WXACXMWYHXOSIX-UHFFFAOYSA-N 0.000 description 2
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical class [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 2
- MIODROMBEUMZIF-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenecyclohexane Chemical compound C1CCCCC1=C1C=CC=C1 MIODROMBEUMZIF-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical class BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 1
- SDPURBHAHVFTGX-UHFFFAOYSA-N 2,7-dichloro-9h-fluorene Chemical class ClC1=CC=C2C3=CC=C(Cl)C=C3CC2=C1 SDPURBHAHVFTGX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention provides a bridged dinuclear metallocene compound for sPP , and a preparation method and application thereof. The structure of the metallocene compound is shown as a formula I:wherein: r1Selected from hydrogen, methyl, methylene, ethyl and phenyl, R2Selected from hydrogen, tert-butyl, bromine and chlorine. The preparation method of the compound comprises the following steps: reacting p-xylene, N-bromosuccinimide and benzoyl peroxide to obtain p-dibromide benzyl; reacting a fulvene compound with a fluorene lithium compound to obtain a bridged fluorene lithium salt; reacting p-dibromide benzyl with bridged fluorecenocene lithium salt to obtain a ligand; and reacting the ligand with n-butyllithium and then zirconium tetrachloride to obtain the bridged dinuclear metallocene compound for sPP. The invention also provides the application of the metallocene compound as a catalyst for catalyzing propylene polymerization reaction.
Description
Technical field
The present invention relates to a kind of sPP bridged binuclear metallocene compound and preparation method thereof and application, belong to Metallocene catalysts technique field.
Background technology
Since Fina company in 1993 since liquid phase annular-pipe reactor scale up test goes out sPP, the offshore company such as Basell, Huntsman, Dow, ExxonMobil company and Mitsui Dong Ya company, bright dipping petro-chemical corporation is successively devoted to the exploitation of sPP.Current Fina company and Basell, ExxonMobil, Japanese bright dipping petro-chemical corporation have achieved the suitability for industrialized production of sPP.
This monokaryon metallocene catalyst becomes the emphasis of various countries scientist research, and all respects of this research field by the monokaryon catalyzer nearly cover of patent protection, are difficult to large original creativity.With certain abutment, bridging type monokaryon metallocene compound is coupled together, obtaining doube bridge metallocene is a brand-new research field.
Alt, Helmut G (Helmut G.Alt, Rainer Ernst.Dinuclear ansa zirconocene complexes asdual-site catalysts for the polymerization of ethylene [J] .Journal of Molecular Catalysis A:Chemical 195. (2003) .11-27) synthesize this catalyzer of bridged binuclear, its structure is such as formula shown in VI, for propylene polymerization, active (93000kg mol
-1h
-1atm
-1) than corresponding monokaryon metallocene catalyst Me
2si (2-Me-I-Ind) (2-Me-4-Ph-I-Ind) ZrCl
2(LZrCl
2=446000kg mol
-1h
-1atm
-1) low, but the polyacrylic molecular weight of preparation adds, and atactic degree too increases (6.1wt%versus<0.2wt%forLZrCl
2).
Afterwards, Alt (Deppner, M.Alkylidenverbr ü ckte, symmetrische, zweikernigeMetallocenkomplexe als Katalysatoren f ü r die Propylenpolymerisation [J] .Journal oforganometallic chemistry.2005,690 (12): 2861-2871.) have also been made corresponding research, synthesized the asymmetric binuclear metallocene catalyzer of carbon bridging of different lengths, such as structure is such as formula the compound shown in VII.When carbon bridge length is less than 5 carbon atoms, the molecular weight distribution of resulting polymers is wider (MWD>10).Find in propylene polymerization, gained polyacrylic complete be 9-11% with degree of isotacticity.
Stephan Jungling (J ü ngling, S., R.M ü llhaupt and H.Plenio.Cooperative effects inbinuclear zirconocenes:their synthesis and use as catalyst in propene polym-erization [J] .Journal of organometallic chemistry.1993,460 (2): 191-195.) synthesized a series of benzene bridged binuclear Zirconocene, such as structure is such as formula the compound shown in VIII.Compared with monokaryon catalyst system, catalyzing propone polymerization activity reduces (2.6 × 10
5gPP/mol Zr h, monokaryon catalyst system is 3 × 10
5gPP/mol Zr h), molecular weight reduces (GPC:Mn=2200g/mol, monokaryon catalyst system Mn=3400g/mol).And contrary with monokaryon catalyst system, along with the increase of AI/Zr ratio, molecular weight reduces.
Sierra (Cano Sierra, J.Formation of Dinuclear Titanium and Zirconium Complexes byOlefin Metathesis-Catalytic Preparation of Organometallic Catalyst Systems [J] .Chemistry-A European Journal.2003, 9 (15): 3618-3622.) etc. dinuclear catalyst has been synthesized, its structure is such as formula shown in IX, this catalyst vinyl polymerization, under room temperature (25 DEG C), activity is quite low, when temperature is 60 DEG C, active very high, catalyzing propone is polymerized, at room temperature (25 DEG C) and 60 DEG C, activity is common level, molecular weight is quite low, under room temperature, 36% isotatic polypropylene can be obtained, at 60 DEG C, obtain 12% Atactic Polypropelene.
Visible, the research of doube bridge metallocene has become the research core of this area, develops novel bridged binuclear metallocene compound and is still one of this area problem demanding prompt solution.
Summary of the invention
For solving the problems of the technologies described above, the object of the invention is to provide a kind of sPP bridged binuclear metallocene compound and preparation method thereof and application.Bridged binuclear metallocene compound provided by the invention is high as the activity of catalyzer, can be used in catalyzing propone polyreaction.
For achieving the above object, the invention provides a kind of sPP bridged binuclear metallocene compound, its structure is such as formula shown in I:
Wherein: R
1be selected from hydrogen (H), methyl (-CH
3), methylene radical (-C
2h
5), ethyl
with phenyl (-C
6h
5), R
2be selected from hydrogen, the tertiary butyl (
tbu), bromine (Br) and chlorine (Cl).
According to the specific embodiment of the present invention, preferably, above-mentioned sPP bridged binuclear metallocene compound includes, but are not limited to:
[(CH
3)
2C(C
5H
3)(C
13H
8)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(C
6H
5)
2C(C
5H
3)(C
13H
8)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(CH
2)
5C(C
5H
3)(C
13H
8)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(CH
3)
2C(C
5H
3)((
tBu)
2C
13H
6)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(C
6H
5)
2C(C
5H
3)((
tBu)
2C
13H
6)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(CH
2)
5c (C
5h
3) (Cl
2c
13h
6) ZrCl
2]
2(CH
2c
6h
4cH
2) and
[(CH
3)
2C(C
5H
3)(Br
2C
13H
6)ZrCl
2]
2(CH
2C
6H
4CH
2)。
The present invention introduces methyl, methylene radical, ethyl, phenyl on the carbon abutment connecting luxuriant ring and fluorenes ring, fluorenyl is introduced the tertiary butyl, bromine, chlorine, obtain a series of bridged binuclear metallocene compound, complex compound yield can be improved, when adopting this compound for catalysis propylene polymerization, activity is higher, and a normality is also higher.
The sterie configuration of bridged binuclear metallocene compound of the present invention is stablized, the C atom connecting Cp (cyclopentadienyl) and Flu (fluorenyl) limits the rotation of luxuriant ring, if there is no C bridging between Cp and Flu, luxuriant ring can rotate freely, central metal surrounding space configuration is caused not fix, after bridging, the sterie configuration of luxuriant ring is just relatively fixing; With connecting two Cp bridges to dibenzyl, just make its sterie configuration more stable, define the constrained geometry configuration metallocene compound of carbon bridging, be conducive to Propylene Selectivity polymerization.
On the other hand, the present invention also provides a kind of preparation method of above-mentioned sPP bridged binuclear metallocene compound, and it comprises the following steps:
(1) p-Xylol, N-bromo-succinimide (NBS) and benzoyl peroxide (BPO) is made to react, to prepare cyclite;
(2) fulvene compounds and fluorenes lithium compounds is made to react, to prepare the luxuriant lithium salts of bridging fluorenes;
The structure of described fulvene compounds such as formula shown in II,
Wherein: R
1hydrogen, methyl, methylene radical, ethyl and phenyl.
The structure of described fluorenes lithium compounds as shown in formula III,
Wherein, R
2hydrogen, methyl, methylene radical, ethyl and phenyl.
(3) what make step (1) obtain reacts the luxuriant lithium salts of bridging fluorenes that cyclite and step (2) obtain, to prepare ligand L;
The structure of described ligand L is such as formula shown in IV:
Wherein: R
1be selected from hydrogen, methyl, methylene radical, ethyl and phenyl, R
2be selected from hydrogen, the tertiary butyl, bromine and chlorine.
(4) make ligand L and n-Butyl Lithium (
nbuLi) be obtained by reacting four lithium salts, then react with zirconium tetrachloride, to prepare described sPP bridged binuclear metallocene compound.
In above-mentioned preparation method; preferably; step (1) comprising: argon shield and 70 DEG C at 90 DEG C; take tetracol phenixin as solvent; make p-Xylol, N-bromo-succinimide and benzoyl peroxide back flow reaction 10-30 hour; wherein the mass ratio of p-Xylol, N-bromo-succinimide and benzoyl peroxide is 5.04:30:2; then 0 DEG C to 40 DEG C is cooled to; filtrate is got after filtration; place 10-24 hour at-40 DEG C to-20 DEG C after; separate out white crystal, be cyclite.
In above-mentioned preparation method, preferably, step (2) comprising: at-40 to 10 DEG C, the diethyl ether solution of fulvene compounds was added drop-wise in the diethyl ether solution of fluorenes lithium compounds in 10 minutes to 30 minutes, wherein the mol ratio of fulvene compounds and fluorenes lithium compounds is 1:1 to 1.3:1, after (about reacting 8 hours) to be precipitated occurs, react 10 to 30 hours again, isolate lower floor's solid (preferably adopting press filtration to be separated), washing (preferably adopts washed with diethylether twice, hexanes wash is once) and after draining, obtain pale pink solid, be the luxuriant lithium salts of bridging fluorenes.
In above-mentioned preparation method, preferably, step (3) comprising: at-40 DEG C at 0 DEG C, the tetrahydrofuran (THF) to cyclite (THF) solution step (1) obtained was added drop-wise in the tetrahydrofuran solution of the luxuriant lithium salts of bridging fluorenes that step (2) obtains in 10 minutes to 30 minutes, wherein, be 1:1 to 1:2.2 to the mol ratio of cyclite and the luxuriant lithium salts of bridging fluorenes, then 30 DEG C are naturally risen to, react and add dilute acid soln after 30 to 50 hours and be hydrolyzed, adjust ph is to neutral (preferably adopting acetic acid), organic phase is got after separatory, aqueous phase extracted with diethyl ether (extraction times can be twice), then merge with organic phase, again through washing (preferably adopting saturated common salt water washing), dry (preferably adopting anhydrous magnesium sulfate drying 6 hours), filter, remove solvent (preferably adopting vacuum to revolve to desolventize or removed under reduced pressure solvent), after column chromatography for separation, obtain mucus, be ligand L.
In above-mentioned preparation method, preferably, step (4) comprising: at-40 DEG C at 0 DEG C, in the tetrahydrofuran solution of ligand L, add the hexane solution of n-Butyl Lithium, wherein the mol ratio of ligand L and n-Butyl Lithium is 1:4 to 1:5, is then warming up to 25 DEG C to 50 DEG C, reaction 20-60 hour, the solid tetrahydrofuran (THF) obtained after separation suspends, and then at-80 DEG C to-70 DEG C, adds ZrCl
42THF, wherein ligand L and ZrCl
4the mol ratio of 2THF is 1:1.8 to 1:2, be warmed up to 20 DEG C to 30 DEG C, reaction 40-60 hour, then remove desolventizing (preferably adopt and drain), with dichloromethane extraction (extraction time can be twice), concentrate, add normal hexane again, then at-40 DEG C to-20 DEG C, crystallization obtains solid, is described sPP bridged binuclear metallocene compound.
In above-mentioned preparation method, preferably, described fluorenes lithium compounds prepares by the following method: at-10 DEG C at 20 DEG C, in the presence of an organic, n-Butyl Lithium is added drop-wise in compound of fluorene class, wherein the mol ratio of n-Butyl Lithium and compound of fluorene class is 1:1 to 1.2:1, then 21 DEG C to 30 DEG C are naturally risen to, after stirring reaction 10-20 hour, solid-liquid separation (preferably adopting press filtration), solid is through washing (preferably adopting n-hexane twice), after draining, obtain described fluorenes lithium compounds, wherein, the structure of described compound of fluorene class is such as formula shown in V:
Wherein, R
2be selected from hydrogen, the tertiary butyl, bromine and chlorine.
On the other hand, the present invention also provides above-mentioned sPP bridged binuclear metallocene compound in propylene polymerization as the application of catalyzer.
In the applications described above, preferably, described sPP bridged binuclear metallocene compound is as Primary Catalysts, and methylaluminoxane (MAO) is as promotor, and the amount ratio of Primary Catalysts and promotor is 500 to 2000.
In the applications described above, described propylene polymerization can carry out in accordance with the following methods: such as, under propylene pressure is 0.1MPa, take toluene as solvent, add the toluene solution containing sPP bridged binuclear metallocene compound, promotor MAO, in the 0.5 hour reaction times at temperature of reaction 0 DEG C, catalyzing propone is polymerized.
The present invention adopts bridged binuclear metallocene catalyst/MAO system, and under the effect of lower ratio promotor, obtain greater activity to propylene polymerization, between polymkeric substance, normality reaches more than 80%.
In sum, the synthetic route of sPP bridged binuclear metallocene compound provided by the invention is simple, and product yield is high, and separation and purification is easy, and need promotor few when being polymerized for catalyzing propone, catalytic activity is high, and between polymkeric substance, normality is high.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Ligand L 1 [(CH
3)
2c (C
5h
4) (C
13h
9)]
2(CH
2c
6h
4cH
2) synthesis
Ligand L 1 [(CH
3)
2c (C
5h
4) (C
13h
9)]
2(CH
2c
6h
4cH
2) synthetic route as follows:
Under argon shield, take tetracol phenixin as solvent, by p-Xylol (5.04g; 47.53mmol), NBS (30g) and BPO (2g) is added in bottle and reacts, and heating, when being heated to 70 DEG C; solid in bottle and liquid start melting, after stable, continue heating; to 80 DEG C; back flow reaction 20 hours, cools, upper strata adularescent solid; the pale yellow clear liquid of lower floor; be cooled to 40 DEG C, filter, get filtrate; put into refrigerator; after 24h, separate out white crystal, about 5g; be cyclite, productive rate 40%.
Add fluorenes (10g, 60.24mmol), normal hexane 100mL, ether 20mL in 200mL Schlenk bottle, at 0 DEG C, slowly drip
nbuLi (36.7mL, 1.64mol/L), has precipitation to generate immediately.Naturally rise to room temperature, stirring reaction to 20 hour, leave standstill, press filtration removing supernatant, solid normal hexane washes 2 times.Drain to obtain yellow solid powder 8g, be fluorenes lithium, productive rate 86.7%.
0 DEG C, by 6,6-dimethyl fulvene (5.11g, ether (40mL) solution 48.18mmol) is added drop-wise in ether (80mL) solution of fluorenes lithium (FluLi) (8g, 48.18mmol), has precipitation to occur after 8h, continue the reaction 20 hours amount of having precipitations to generate, press filtration, solid ether washes twice, washes once with hexane, drain, obtain solid 9.18g, that is, yield 70%.
The luxuriant lithium salts of the above-mentioned bridging fluorenes (15.19mmol) of 4.3g is dissolved in 50mLTHF, yellow general red, under ice bath, slowly drip cyclite (2.01g, THF (40mL) solution (pale yellow) 7.59mmol), naturally room temperature is risen to, afterwards, color is deepened a little, dark red partially yellow, stirring reaction 40 hours vinegar acid for adjusting pH are to neutral, separatory, get organic phase, aqueous phase extracted with diethyl ether twice, merge organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying 6h, filter, vacuum is revolved and is desolventized, column chromatography for separation, obtain 1.47g mucus, be ligand L 1, productive rate 30%.
Complex compound 1 [(CH
3)
2c (C
5h
3) (C
13h
8) ZrCl
2]
2(CH
2c
6h
4cH
2) synthesis
0 DEG C of condition, BuLi (8mmol) is added drop-wise to ligand L 1 (1.29g, in diethyl ether solution 2mmol), have solid to generate, reacting by heating removed supernatant liquid after 40 hours, and solid ether is drained, obtain solid 1.12g, add tetrahydrofuran (THF), under liquid nitrogen ethanol bath-78 DEG C of conditions, add ZrCl
42THF (1.26g, 3.34mmol), rises to room temperature naturally, react 50 hours, elimination supernatant liquid, removal of solvent under reduced pressure, solid with methylene chloride extracts twice (30mL × 2), is concentrated into 20mL, adds normal hexane and adjusts polarity, put in-20 DEG C of refrigerators, separate out yellow substance, press filtration removing supernatant liquor, precipitation is drained, obtain yellow powder 547mg, be complex compound 1, yield 34%.Fusing point: 210 DEG C of decomposition.
1h NMR (δ, ppm, DCCl
3, 400MHz): 7.65-7.67 (m, 4H, ArH), 7.28-7.30 (m, 8H, ArH), 7.12-7.14 (m, 8H, ArH), 7.09-7.15 (m, 4H, CpH), 7.01 (s, 2H, CpH), 3.05 (s, 4H, ArCH
2), 1.18 (s, 12H, CH
3), prove really to have prepared complex compound 1.
Homogeneous catalysis propylene polymerization under normal pressure
Magnetic stir bar will be had, the 100mL there-necked flask ethylene gas of airway replaces 3 times, under nitrogen protection, add toluene 50mL successively, promotor MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 1, propylene gas is passed under normal pressure, polyreaction is started at 0 DEG C, stirring reaction 30min, close propylene gas cylinder, by the acidic alcohol termination reaction of 10%, polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, at 80 DEG C, vacuum-drying is to constant weight, weigh polymer quality 4.2g, polymerization activity 2.1 × 10
6gpolymer/molMh, carry out after removing random thing with dimethylbenzene from
13c NMR characterizes, and calculating is learnt, between the rrrr of the polymkeric substance obtained, normality is up to 85%.
Embodiment 2
Ligand L 2 [(C
6h
5)
2c (C
5h
4) (C
13h
9)]
2(CH
2c
6h
4cH
2) synthesis
Under 0 DEG C of condition, by 6,6-phenylbenzene fulvene (11.08g, ether (40mL) solution 48.18mmol) is added drop-wise to FluLi (8g, in ether (80mL) solution 48.18mmol), there is precipitation to occur after 8 hours, react and precipitate generation in a large number after 20 hours, press filtration is except desolventizing, solid ether washes twice, washes once, drain with hexane, obtain solid 12.41g, productive rate 65%.
The above-mentioned lithium salts (15.19mmol) of 6.18g is dissolved in 50mLTHF, yellow general red, under ice bath, slowly drip dibromo Bian (2.01g, THF (40mL) solution (pale yellow) 7.59mmol), naturally rise to room temperature, solution colour is deepened a little a little afterwards, dark red partially yellow, react two days.Hydrolysis acetic acid regulates ph to neutral, and separatory, gets organic phase, aqueous phase extracted with diethyl ether twice, merges organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying 6h, and filter, vacuum is revolved and desolventized, column chromatography for separation, obtains 2.31g mucus, productive rate 34%.
Complex compound 2 [(C
6h
5)
2c (C
5h
3) (C
13h
8) ZrCl
2]
2(CH
2c
6h
4cH
2) synthesis
Under ice-water bath condition,
nbuLi (8mmol) is added drop-wise to ligand L 2 (1.788g, in diethyl ether solution 2mmol), there is solid to generate, reflux anti-40 hours, supernatant liquid is removed in press filtration, wash once with ether, drain, obtain solid 1.62g, add tetrahydrofuran (THF), liquid nitrogen ethanol bath, under-78 DEG C of conditions, adds ZrCl
42THF (1.33g, 3.53mmol), rises to room temperature naturally, react 40 hours, reaction solution is yellow, removal of solvent under reduced pressure, dichloromethane extraction twice (30mL × 2), is concentrated into 20mL, adds normal hexane and adjusts polarity, put in-20 DEG C of refrigerators, separate out yellow substance, press filtration removing supernatant liquor, precipitation is drained, obtain yellow powder 640mg, yield 30%.Fusing point 240 DEG C decomposition.
1h NMR (δ, ppm, DCCl
3, 400MHz): 7.55-7.47 (m, 8H, ArH), 7.31-7.21 (m, 8H, ArH), 7.16-7.10 (m, 4H, ArH), 7.05 (s, 20H, ArH), 7.00-6.92 (m, 4H, CpH), (6.6 s, 2H, CpH), 3.03 (s, 4H, ArCH
2), prove really to have prepared complex compound 2.
Homogeneous catalysis propylene polymerization under normal pressure
Magnetic stir bar will be had, the 100mL there-necked flask ethylene gas of airway replaces 3 times, under nitrogen protection, add toluene 50mL successively, promotor MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 2, propylene gas is passed under normal pressure, polyreaction is started at 0 DEG C, stirring reaction 30min, close propylene gas cylinder, by the acidic alcohol termination reaction of 10%, polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, at 80 DEG C, vacuum-drying is to constant weight, weigh polymer quality 3.0g, polymerization activity 1.5 × 10
6gpolymer/molMh, carry out after removing random thing with dimethylbenzene from
13c NMR characterizes, and calculating is learnt, between the rrrr of the polymkeric substance obtained, normality is up to 84%.
Embodiment 3
Ligand L 3 [(CH
2)
5c (C
5h
4) (C
13h
9)]
2(CH
2c
6h
4cH
2) synthesis
Under ice bath, by 6,6-pentamethylene fulvene (8.89g, ether (40mL) solution 48.18mmol) is added drop-wise in ether (80mL) solution of FluLi (8g, 48.18mmol), does not precipitate generation during dropping, after about 8h, there is precipitation to occur, react and precipitate generation in a large number after 20 hours, press filtration, solid ether washes twice, washes once, drain with hexane, obtain solid 11.49g, productive rate 68%.
The above-mentioned lithium salts (15.19mmol) of 4.91g is dissolved in 50mLTHF, yellow general red, under ice bath, slowly drip dibromo Bian (2.01g, THF (40mL) solution (pale yellow) 7.59mmol), after naturally rising to room temperature, color is deepened a little a little, dark red partially yellow, react 40 hours.Hydrolysis, vinegar acid for adjusting pH is to neutral, and separatory, gets organic phase, aqueous phase extracted with diethyl ether twice, merges organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying 6h, and filter, decompression desolventizes, column chromatography for separation, obtains 1.54g mucus, productive rate 28%.
Complex compound 3 [(CH
2)
5c (C
5h
3) (C
13h
8) ZrCl
2]
2(CH
2c
6h
4cH
2) synthesis
Under ice-water bath condition,
nbuLi (8mmol) is added drop-wise in the diethyl ether solution of part (1.45g, 2mmol), has solid to generate, back flow reaction two days, supernatant liquid is removed in press filtration, washes once, drains, obtain solid 1.32g with ether, add tetrahydrofuran (THF), liquid nitrogen ethanol bath, under-78 DEG C of conditions, add ZrCl
42THF (1.33g, 3.52mmol), rises to room temperature naturally, react 2 days, reaction solution is yellow, removal of solvent under reduced pressure, dichloromethane extraction twice (30mL × 2), is concentrated into 20mL, adds some normal hexanes and adjusts polarity, put in-20 DEG C of refrigerators, separate out yellow substance, press filtration removing supernatant liquor, precipitation is drained, obtain yellow powder 476mg, yield 26%.Fusing point: 270 DEG C of decomposition.
1h NMR (δ, ppm, DCCl
3, 400MHz): 7.66-7.68 (m, 4H, ArH), 7.29-7.31 (m, 8H, ArH), 7.17-7.20 (m, 8H, ArH), 7.10-7.15 (m, 4H, CpH), 7.03 (s, 2H, CpH), 3.04 (s, 4H, ArCH
2), 0.80-0.83 (m, 6H, CH
2), 1.12-1.19 (m, 8H, CH
2), 1.48-1.49 (m, 6H, CH
2), prove really to have prepared complex compound 3.
Homogeneous catalysis propylene polymerization under normal pressure
Magnetic stir bar will be had, the 100mL there-necked flask ethylene gas of airway replaces 3 times, under nitrogen protection, add toluene 50mL successively, promotor MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 3, propylene gas is passed under normal pressure, polyreaction is started at 0 DEG C, stirring reaction 30min, close propylene gas cylinder, by the acidic alcohol termination reaction of 10%, polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, at 80 DEG C, vacuum-drying is to constant weight, weigh polymer quality 2.2g, polymerization activity 1.1 × 10
6gpolymer/molMh, carry out after removing random thing with dimethylbenzene from
13c NMR characterizes, and calculating is learnt, between the rrrr of the polymkeric substance obtained, normality is up to 82%.
Embodiment 4
Ligand L 4 [(CH
3)
2c (C
5h
4) ((
tbu)
2c
13h
7)]
2(CH
2c
6h
4cH
2) synthesis
Under ice bath, by 6,6-dimethyl fulvene (5.11g, ether (40mL) solution 48.18mmol) is added drop-wise in ether (80mL) solution of 2,7-di-tert-butyl-fluorene lithium (13.39g, 48.18mmol), do not precipitate generation during dropping, after about 8h, have precipitation to occur, the next morning, precipitate generation in a large number, press filtration, solid ether washes twice, washes once, drain with hexane, obtain solid 14.57g, productive rate 70%.
The above-mentioned lithium salts (15.19mmol) of 6.5g is dissolved in 50mLTHF, yellow general red, under ice bath, be slowly added drop-wise to THF (40mL) solution (pale yellow) of dibromo Bian (2.01g, 7.59mmol), there is no considerable change, naturally rise to room temperature, afterwards, color is deepened a little a little, dark red partially yellow, react two days.Hydrolysis, vinegar acid for adjusting pH is to neutral, and separatory, gets organic phase, aqueous phase extracted with diethyl ether twice, merges organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying 6h, and filter, vacuum is revolved and desolventized, and column chromatography for separation obtains 2.06g, yield 28%.
Complex compound 4 [(CH
3)
2c (C
5h
3) ((
tbu)
2c
13h
6) ZrCl
2]
2(CH
2c
6h
4cH
2) synthesis
Under 0 DEG C of condition,
nbuLi (8mmol) is added drop-wise in the diethyl ether solution of part (1.93g, 2mmol), has solid to generate, back flow reaction two days, supernatant liquid is removed in press filtration, washes once, drains, obtain solid 1.72g with ether, add tetrahydrofuran (THF), liquid nitrogen ethanol bath, under-78 DEG C of conditions, add ZrCl
22THF (1.310g, 3.47mmol), rises to room temperature naturally, react 2 days, reaction solution is yellow, removal of solvent under reduced pressure, dichloromethane extraction twice (30mL × 2), is concentrated into 20mL, adds some normal hexanes and adjusts polarity, put in-20 DEG C of refrigerators, separate out yellow substance, press filtration removing supernatant liquor, precipitation is drained, obtain yellow powder 624mg, yield 28%.
1h NMR (δ, ppm, DCCl
3, 400MHz): 7.71 (s, 4H, ArH), 7.65-7.60 (m, 4H, ArH), 7.43-7.39 (m, 4H, ArH), 7.14-7.11 (m, 4H, ArH), 6.93-6.87 (m, 4H, CpH), (6.81-6.85 s, 2H, CpH), 3.04 (s, 4H, ArCH
2), 1.29 (s, 1.10 (s, 12H, CpCH
3) .1.14 (s, 36H ,-CMe
3), prove really to have prepared complex compound 4.
Homogeneous catalysis propylene polymerization under normal pressure
Magnetic stir bar will be had, the 100mL there-necked flask ethylene gas of airway replaces 3 times, under nitrogen protection, add toluene 50mL successively, promotor MAO2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 4, propylene gas is passed under normal pressure, polyreaction is started at 0 DEG C, stirring reaction 30min, close propylene gas cylinder, by the acidic alcohol termination reaction of 10%, polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, at 80 DEG C, vacuum-drying is to constant weight, weigh polymer quality 5.0g, polymerization activity 2.5 × 10
6gpolymer/molMh, carry out after removing random thing with dimethylbenzene from
13c NMR characterizes, and calculating is learnt, between the rrrr of the polymkeric substance obtained, normality is up to 82%.
Embodiment 5
Ligand L 5 [(C
6h
5)
2c (C
5h
4) ((
tbu)
2c
13h
7)]
2(CH
2c
6h
4cH
2) synthesis
Under condition of ice bath, by 6,6-phenylbenzene fulvene (11.08g, ether (40mL) solution 48.18mmol) is added drop-wise in ether (80mL) solution of 2,7-di-tert-butyl-fluorene lithium (13.39g, 48.18mmol), after 8h, there is precipitation to occur, continue reaction after 20 hours, a large amount of precipitation generates, press filtration, and solid ether washes twice, wash once with hexane, drain, obtain solid 9.18g, yield 70%.
The above-mentioned lithium salts (15.19mmol) of 7.88g is dissolved in 50mLTHF, yellow general red, under ice bath, slowly drip dibromo Bian (2.01g, THF (40mL) solution (pale yellow) 7.59mmol), after naturally rising to room temperature, color is deepened a little a little, dark red partially yellow, react 40 hours.Hydrolysis, vinegar acid for adjusting pH is to neutral, and separatory, gets organic phase, aqueous phase extracted with diethyl ether twice, merges organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying 6h, and filter, vacuum is revolved and desolventized, column chromatography for separation, obtains 2.55g mucus, productive rate 30%.
Complex compound 5 [(C
6h
5)
2c (C
5h
3) ((
tbu)
2c
13h
6) ZrCl
2]
2(CH
2c
6h
4cH
2) synthesis
Under ice-water bath condition,
nbuLi (8mmol) is added drop-wise to part (2.24g, in diethyl ether solution 2mmol), solid is had to generate, back flow reaction 45 hours, supernatant liquid is removed in press filtration, precipitation ether is washed once, drains, and obtains solid 2.04g, add tetrahydrofuran (THF), liquid nitrogen ethanol bath, under-48 DEG C of conditions, adds ZrCl
22THF (1.347g, 3.57mmol), rises to room temperature naturally, react 2 days, reaction solution is yellow, removal of solvent under reduced pressure, dichloromethane extraction twice (30mL × 2), is concentrated into 20mL, adds normal hexane and adjusts polarity, put in-20 DEG C of refrigerators, separate out yellow substance, press filtration removing supernatant liquor, precipitation is drained, obtain yellow powder 740mg, yield 29%.
1h NMR (δ, ppm, DCCl
3, 400MHz): 7.68 (s, 4H, ArH), 7.605-7.55 (m, 4H, ArH), 7.40-7.34 (m, 4H, ArH), 7.11-7.07 (m, 4H, ArH), 7.03 (s, 20H, ArH), 6.91-6.80 (m, 4H, CpH), 6.56 (s, 2H, CpH), 3.07 (s, 4H, ArCH
2), 1.15 (s, 36H, CMe
3), prove really to have prepared complex compound 5.
Homogeneous catalysis propylene polymerization under normal pressure
Magnetic stir bar will be had, the 100mL there-necked flask ethylene gas of airway replaces 3 times, under nitrogen protection, add toluene 50mL successively, promotor MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 5, propylene gas is passed under normal pressure, polyreaction is started at 0 DEG C, stirring reaction 30min, close propylene gas cylinder, by the acidic alcohol termination reaction of 10%, polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, at 80 DEG C, vacuum-drying is to constant weight, weigh polymer quality 5.6g, polymerization activity 2.8 × 10
6gpolymer/molMh, carry out after removing random thing with dimethylbenzene from
13c NMR characterizes, and calculating is learnt, between the rrrr of the polymkeric substance obtained, normality is up to 81%.
Embodiment 6
Ligand L 6 [(CH
2)
5c (C
5h
4) (Cl
2c
13h
7)]
2(CH
2c
6h
4cH
2) synthesis
Under ice bath, by 6,6-pentamethylene fulvene (8.89g, ether (40mL) solution 48.18mmol) is added drop-wise in ether (80mL) solution of 2,7-dichloro fluorenes (11.18g, 48.18mmol), precipitation occurs slowly, precipitate generation in a large number after 24 hours, press filtration, solid ether washes twice, wash once with hexane, drain, obtain solid 11.49g, productive rate 68%.
The above-mentioned lithium salts (15.19mmol) of 5.94g is dissolved in 50mLTHF, yellow general red, under ice bath, slowly drip dibromo Bian (2.01g, THF (40mL) solution (pale yellow) 7.59mmol), rises to room temperature naturally, reacts 50 hours afterwards.Hydrolysis, vinegar acid for adjusting pH is to neutral, and separatory, gets organic phase, aqueous phase extracted with diethyl ether twice, merges organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying 6h, and filter, decompression desolventizes, column chromatography for separation, obtains 1.83g mucus, productive rate 28%.
Complex compound 6 [(CH
2)
5c (C
5h
3) (Cl
2c
13h
6) ZrCl
2]
2(CH
2c
6h
4cH
2) synthesis
Under ice-water bath condition,
nbuLi (8mmol) is added drop-wise to part (1.72g, in diethyl ether solution 2mmol), solid is had to generate, back flow reaction 50 hours, supernatant liquid is removed in press filtration, wash once with ether, drain, obtain solid 1.62g, add tetrahydrofuran (THF), liquid nitrogen ethanol bath, under-50 DEG C of conditions, adds ZrCl
22THF (1.381g, 3.66mmol), rises to room temperature naturally, react 55 hours, reaction solution is yellow, removal of solvent under reduced pressure, dichloromethane extraction twice (30mL × 2), is concentrated into 20mL, adds normal hexane and adjusts polarity, put in-20 DEG C of refrigerators, separate out yellow substance, press filtration removing supernatant liquor, precipitation is drained, obtain yellow powder 645mg, yield 30%.
1h NMR (δ, ppm, DCCl
3, 400MHz): 7.72-7.76 (m, 4H, ArH), 7.64 (s, 4H, ArH), 7.42-7.38 (m, 4H, ArH), 7.12-7.11 (m, 4H, ArH), 7.07-7.05 (m, 4H, CpH), 6.97 (s, 2H, CpH), 3.01 (s, 4H, ArCH
2), 0.78-0.80 (m, 6H, CH
2), 1.10-1.16 (m, 8H, CH
2), 1.40-1.37 (m, 6H, CH
2), prove really to have prepared complex compound 6.
Homogeneous catalysis propylene polymerization under normal pressure
Magnetic stir bar will be had, the 100mL there-necked flask ethylene gas of airway replaces 3 times, under nitrogen protection, add toluene 50mL successively, promotor MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 6, propylene gas is passed under normal pressure, polyreaction is started at 0 DEG C, stirring reaction 30min, close propylene gas cylinder, by the acidic alcohol termination reaction of 10%, polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, at 80 DEG C, vacuum-drying is to constant weight, weigh polymer quality 1.7g, polymerization activity 8.5 × 10
5gpolymer/molMh, carry out after removing random thing with dimethylbenzene from
13c NMR characterizes, and calculating is learnt, between the rrrr of the polymkeric substance obtained, normality is up to 80%.
Embodiment 7
Ligand L 7 [(CH
3)
2c (C
5h
4) (Br
2c
13h
7)]
2(CH
2c
6h
4cH
2) synthesis
Under ice bath, by 6-methyl, 6-ethyl fulvene (5.78g, ether (40mL) solution 48.18mmol) is added drop-wise in ether (80mL) solution of 2,7-dibromo fluorenes (15.56g, 48.18mmol), do not precipitate generation during dropping, after about 8h, have precipitation to occur, the next morning, precipitate generation in a large number, press filtration, solid ether washes twice, washes once, drain with hexane, obtain solid 9.92g, productive rate 72%.
The lithium salts (15.19mmol) of 6.88g is dissolved in 50mLTHF, yellow general red, under ice bath, slowly be added drop-wise to dibromo Bian (2.01g, THF (40mL) solution (pale yellow) 7.59mmol), after naturally rising to room temperature, reacts 65 hours.Hydrolysis, acetic acid regulates ph to neutral, and separatory, gets organic phase, aqueous phase extracted with diethyl ether twice, merges organic phase, saturated common salt water washing, anhydrous magnesium sulfate drying 6h, and filter, vacuum is revolved and desolventized, column chromatography for separation, obtains 2.1g mucus, productive rate 28%.
Complex compound 7 [(CH
3)
2c (C
5h
3) (Br
2c
13h
6) ZrCl
2]
2(CH
2c
6h
4cH
2) synthesis
Under ice-water bath condition,
nbuLi (8mmol) is added drop-wise in the diethyl ether solution of part (1.97g, 2mmol), has solid to generate, back flow reaction two days, supernatant liquid is removed in press filtration, washes once, drains, obtain solid 1.83g with ether, add tetrahydrofuran (THF), liquid nitrogen ethanol bath, under-60 DEG C of conditions, add ZrCl
22THF (1.366g, 3.62mmol), rises to room temperature naturally, react 2 days, reaction solution is yellow, removal of solvent under reduced pressure, dichloromethane extraction twice (30mL × 2), is concentrated into 20mL, adds some normal hexanes and adjusts polarity, put in-20 DEG C of refrigerators, separate out yellow substance, press filtration removing supernatant liquor, precipitation is drained, obtain yellow powder 730mg, yield 31%.
1h NMR (δ, ppm, DCCl
3, 400MHz): 7.70 (s, 4H, ArH), 7.60-7.55 (m, 4H, ArH), 7.44-7.50 (m, 4H, ArH), 7.16-7.19 (m, 4H, ArH), 7.01-7.06 (m, 4H, CpH), (6.97 s, 2H, CpH), 3.01 (s, 4H, ArCH
2), 1.12 (s, 12H, CH
3), prove really to have prepared complex compound 7.
Homogeneous catalysis propylene polymerization under normal pressure
Magnetic stir bar will be had, the 100mL there-necked flask ethylene gas of airway replaces 3 times, under nitrogen protection, add toluene 50mL successively, promotor MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 7, propylene gas is passed under normal pressure, polyreaction is started at 0 DEG C, stirring reaction 30min, close propylene gas cylinder, by the acidic alcohol termination reaction of 10%, polymkeric substance is transferred in beaker, hold over night, to filter and with the abundant washing copolymer of ethanol, at 80 DEG C, vacuum-drying is to constant weight, weigh polymer quality 1.92g, polymerization activity 9.6 × 10
5gpolymer/molMh, carry out after removing random thing with dimethylbenzene from
13c NMR characterizes, and calculating is learnt, between the rrrr of the polymkeric substance obtained, normality is up to 82%.
Claims (10)
1. a sPP bridged binuclear metallocene compound, its structure is such as formula shown in I:
formula I,
Wherein: R
1be selected from hydrogen, methyl, methylene radical, ethyl and phenyl, R
2be selected from hydrogen, the tertiary butyl, bromine and chlorine.
2. sPP bridged binuclear metallocene compound according to claim 1, it comprises:
[(CH
3)
2C(C
5H
3)(C
13H
8)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(C
6H
5)
2C(C
5H
3)(C
13H
8)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(CH
2)
5C(C
5H
3)(C
13H
8)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(CH
3)
2C(C
5H
3)((
tBu)
2C
13H
6)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(C
6H
5)
2C(C
5H
3)((
tBu)
2C
13H
6)ZrCl
2]
2(CH
2C
6H
4CH
2)、
[(CH
2)
5c (C
5h
3) (Cl
2c
13h
6) ZrCl
2]
2(CH
2c
6h
4cH
2) and
[(CH
3)
2C(C
5H
3)(Br
2C
13H
6)ZrCl
2]
2(CH
2C
6H
4CH
2)。
3. the preparation method for bridged binuclear metallocene compound of the sPP described in claim 1 or 2, it comprises the following steps:
(1) p-Xylol, N-bromo-succinimide and benzoyl peroxide is made to react, to prepare cyclite;
(2) fulvene compounds and fluorenes lithium compounds is made to react, to prepare the luxuriant lithium salts of bridging fluorenes;
The structure of described fulvene compounds such as formula shown in II,
formula II,
Wherein: R
1be selected from hydrogen, methyl, methylene radical, ethyl and phenyl;
The structure of described fluorenes lithium compounds as shown in formula III,
formula III,
Wherein, R
2hydrogen, the tertiary butyl, bromine and chlorine;
(3) what make step (1) obtain reacts the luxuriant lithium salts of bridging fluorenes that cyclite and step (2) obtain, to prepare ligand L;
The structure of described ligand L is such as formula shown in IV:
formula IV,
Wherein: R
1be selected from hydrogen, methyl, methylene radical, ethyl and phenyl, R
2be selected from hydrogen, the tertiary butyl, bromine and chlorine;
(4) make ligand L and n-Butyl Lithium be obtained by reacting four lithium salts, then react with zirconium tetrachloride, to prepare described sPP bridged binuclear metallocene compound.
4. preparation method according to claim 3; wherein; step (1) comprising: argon shield and 70 DEG C at 90 DEG C; take tetracol phenixin as solvent; make p-Xylol, N-bromo-succinimide and benzoyl peroxide back flow reaction 10-30 hour; wherein the mass ratio of p-Xylol, N-bromo-succinimide and benzoyl peroxide is 5.04:30:2; then 0 DEG C to 40 DEG C is cooled to; filtrate is got after filtration; place 10-24 hour at-40 DEG C to-20 DEG C after; separate out white crystal, be cyclite.
5. preparation method according to claim 3, wherein, step (2) comprising: at-40 to 10 DEG C, is added drop-wise in the diethyl ether solution of fluorenes lithium compounds by the diethyl ether solution of fulvene compounds in 10 minutes to 30 minutes, and wherein the mol ratio of fulvene compounds and fluorenes lithium compounds is 1:1 to 1.3:1, after appearance to be precipitated, react 10 to 30 hours again, isolate lower floor's solid, to wash and after draining, obtain pale pink solid, be the luxuriant lithium salts of bridging fluorenes.
6. preparation method according to claim 3, wherein, step (3) comprising: at-40 DEG C at 0 DEG C, the tetrahydrofuran solution to cyclite step (1) obtained was added drop-wise in the tetrahydrofuran solution of the luxuriant lithium salts of bridging fluorenes that step (2) obtains in 10 minutes to 30 minutes, wherein, be 1:1 to 1:2.2 to the mol ratio of cyclite and the luxuriant lithium salts of bridging fluorenes, then 30 DEG C are naturally risen to, react and add dilute acid soln after 30 to 50 hours and be hydrolyzed, adjust ph is to neutral, organic phase is got after separatory, aqueous phase extracted with diethyl ether, then merge with organic phase, again through washing, dry, filter, remove solvent, after column chromatography for separation, obtain mucus, be ligand L.
7. preparation method according to claim 3, wherein, step (4) comprising: at-40 DEG C at 0 DEG C, in the tetrahydrofuran solution of ligand L, add the hexane solution of n-Butyl Lithium, wherein the mol ratio of ligand L and n-Butyl Lithium is 1:4 to 1:5, is then warming up to 25 DEG C to 50 DEG C, reaction 20-60 hour, the solid tetrahydrofuran (THF) obtained after separation suspends, and then at-80 DEG C to-70 DEG C, adds ZrCl
42THF, wherein ligand L and ZrCl
4the mol ratio of 2THF is 1:1.8 to 1:2, is warmed up to 20 DEG C to 30 DEG C, reaction 40-60 hour, then remove desolventizing, with dichloromethane extraction, concentrate, add normal hexane again, then at-40 DEG C to-20 DEG C, crystallization obtains solid, is described sPP bridged binuclear metallocene compound.
8. the preparation method according to claim 3 or 5, wherein, described fluorenes lithium compounds prepares by the following method: at-10 DEG C at 20 DEG C, in the presence of an organic, n-Butyl Lithium is added drop-wise in compound of fluorene class, wherein the mol ratio of n-Butyl Lithium and compound of fluorene class is 1:1 to 1.2:1, then 21 DEG C to 30 DEG C are naturally risen to, after stirring reaction 10-20 hour, solid-liquid separation, solid, after washing, draining, obtains described fluorenes lithium compounds, wherein, the structure of described compound of fluorene class is such as formula shown in V:
formula V,
Wherein, R
2be selected from hydrogen, the tertiary butyl, bromine and chlorine.
9. the bridged binuclear metallocene compound application as catalyzer in propylene polymerization of the sPP described in claim 1 or 2.
10. application according to claim 9, wherein, described sPP bridged binuclear metallocene compound is as Primary Catalysts, and methylaluminoxane is as promotor, and the mol ratio of described Primary Catalysts and described promotor is 500 to 2000.
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